CN113828342B - Cu-Pd-CeO 2 /γ-Al 2 O 3 Preparation of @ NP catalyst and synthesis of benzopyrazine compounds - Google Patents
Cu-Pd-CeO 2 /γ-Al 2 O 3 Preparation of @ NP catalyst and synthesis of benzopyrazine compounds Download PDFInfo
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Abstract
The invention discloses Cu-Pd-CeO 2 /γ‑Al 2 O 3 Preparation of @ NP catalyst and synthesis of benzopyrazine compounds. The Cu-Pd-CeO 2 /γ‑Al 2 O 3 The preparation method of the @ NP catalyst comprises the following steps: (1) Preparation of CeO 2 /γ‑Al 2 O 3 A carrier; (2) Preparation of CeO 2 /γ‑Al 2 O 3 The @ NP vector; (3) Preparing Cu-Pd-CeO by an impregnation method 2 /γ‑Al 2 O 3 @ NP catalyst. The invention also provides a method for synthesizing the benzopyrazines shown in the formula (III) and the derivatives thereof by a one-pot method, wherein the method takes the o-nitroaniline compound shown in the formula (I) and the fatty diol compound shown in the formula (II) as raw materials, and the raw materials are subjected to solvent-free reaction in the presence of Cu-Pd-CeO 2 /γ‑Al 2 O 3 The benzopyrazine compound shown in the formula (III) is synthesized by a one-pot method under the combined action of a @ NP catalyst and alkali. The Cu-Pd-CeO of the invention 2 /γ‑Al 2 O 3 @ NP catalyst loading CeO while increasing the number of basic sites by doping N and P 2 Assist in proton extraction and increase dehydrogenation activity, thereby providing product selectivity.
Description
(I) technical field
The invention relates to Cu-Pd-CeO 2 /γ-Al 2 O 3 A preparation method of a @ NP catalyst and a method for synthesizing a benzopyrazine compound by using the catalyst.
(II) background of the invention
The benzopyrazine, also known as quinoxaline, is an important nitrogen-containing organic heterocyclic compound, and derivatives thereof are important organic drug synthesis intermediates, and have wide pharmacological and biological activities, such as antibiosis, antivirus, anticancer, antitumor and the like; therefore, synthesis of benzopyrazines is of great interest.
The traditional synthesis method of benzopyrazine and derivatives thereof is to synthesize benzopyrazine and derivatives thereof by condensation reaction of o-dicarbonyl compound with high activity and o-diamine. References [ Chiguru Srinivas, chebolu Naga Sesha Sai Pavan Kumar, vaidya Jayathirth Rao, srinivasan Palaniappan,2006,265 (2007): 227-230 reports that when polyaniline sulfate is used as a catalyst and 1, 2-dichloroethane is used as a solvent, stirring and reacting are carried out for 30min at room temperature, and glyoxal and o-phenylenediamine are used as raw materials to synthesize quinoxaline, the yield can reach 85%. Literature [ Thanh Binh Nguyen, ludmila emolenko, ali Al-Mourabit,2015,47: 1741-1748 it is reported that the yield of benzopyrazine synthesized from o-nitroaniline and ethylene glycol by using ferric chloride and sodium sulfide as catalysts, water as solvent, reaction temperature of 140-150 deg.C under nitrogen atmosphere and stirring for 24h, can reach 67%; the 2, 3-dimethyl benzopyrazine is synthesized by taking o-nitroaniline and 2, 3-butanediol as raw materials, and the yield can reach 75%. The method uses o-nitroaniline as the raw material, so that the raw material cost is reduced, but the product yield is not high. Documents [ Feng Xie, min Zhang, huangfeng Jiang, mengmeng Chen, green Chemistry,2015,17:279-284 ] reports that the yield of 2-methylbenzopyrazine can reach 74% by using ruthenium carbonyl as a catalyst, 1, 3-bis (diphenylphosphino) propane as a ligand, cesium hydroxide monohydrate as an alkali auxiliary agent, tert-amyl alcohol as a solvent, reacting at 150 ℃ under a nitrogen atmosphere and stirring for 8-12 h, and synthesizing the 2-methylbenzopyrazine by using o-nitroaniline and 1, 2-propanediol as raw materials; the 2, 3-dimethyl benzopyrazine is synthesized by taking o-nitroaniline and 2, 3-butanediol as raw materials, and the yield can reach 82%. The method also uses o-nitroaniline as the raw material to reduce the raw material cost, but the product yield is still not high. Literature [ Kaushik Chakrabarti, milan Maji, sabuj Kundu, green Chemistry,2019,21:1999-2004 reports that the synthesis of 2-methylbenzopyrazine by using iridium with 2-hydroxypyridyl complex as catalyst, potassium hydroxide as alkali assistant and water as solvent, at 120 deg.C and with stirring for 24h, using o-nitroaniline and 1, 2-propylene glycol as raw materials, the yield can reach 87%; the 2, 3-dimethyl benzopyrazine is synthesized by taking o-nitroaniline and 2, 3-butanediol as raw materials, and the yield can reach 90%. The method has considerable yield, but the adopted homogeneous catalyst is not beneficial to industrial production. Literature [ Sujan tree, kassturi Ganguli, kalipada Jana, sabuj Kundu,2018,54:6883-6886 ] reports that the yield of 2-methylbenzopyrazine is up to 75% by using a Co (NNN) complex as a catalyst, cesium hydroxide monohydrate as an alkali assistant and toluene as a solvent, stirring at a reaction temperature of 150 ℃ for 24 hours and using o-nitroaniline and 1, 2-propylene glycol as raw materials; the 2, 3-dimethyl benzopyrazine is synthesized by taking o-nitroaniline and 2, 3-butanediol as raw materials, and the yield is up to 96%. The method has the same yield, but still adopts homogeneous catalyst which is not beneficial to industrial production and uses organic solvent which is not environment-friendly. Document [ Sujan Tree, dibyajoti Panja, sabuj Kundu,2020,85:2775-2784 reports that the yield of 2-methylbenzopyrazine synthesized by using nickel bromide complexed with o-phenanthrene as a catalyst, cesium hydroxide monohydrate as an alkali assistant and toluene as a solvent at 150 ℃ under an argon atmosphere and stirring for 24 hours can reach 93 percent by using o-nitroaniline and 1, 2-propylene glycol as raw materials; the 2, 3-dimethyl benzopyrazine is synthesized by taking o-nitroaniline and 2, 3-butanediol as raw materials, and the yield is as high as 94%. The method has objective yield, but uses a homogeneous catalyst which is not beneficial to industrial production, and uses a large amount of environment-unfriendly organic solvent for a small amount of reactants. Documents [ Dibyajyoti Panja, bhaskan Paul, bhovaneshwari balasubramaniamam, raju k. Gupta, sabuj Kundu,2020,137:105927 reports that carbon-supported cobalt is used to cooperate with o-diazophenanthrene as a catalyst, cesium hydroxide monohydrate is used as an alkali assistant, toluene is used as a solvent, stirring is carried out for 24 hours at 150 ℃ under an argon atmosphere, o-nitroaniline and 1, 2-propylene glycol are used as raw materials to synthesize 2-methylbenzopyrazine, and the yield can reach 93%; the 2, 3-dimethyl benzopyrazine is synthesized by taking o-nitroaniline and 2, 3-butanediol as raw materials, and the yield reaches 96%. The method has objective yield, uses a heterogeneous catalyst which is beneficial to industrial production, but uses a large amount of environmentally unfriendly organic solvent for a small amount of reactants.
As described above, in the conventional techniques for synthesizing quinoxaline and derivatives thereof by chemical methods, expensive 1, 2-dicarbonyl compounds and aromatic 1, 2-diamines are used as raw materials. The synthesis method usually adopts a transition metal complex as a catalyst, which causes difficult separation and recovery of the catalyst, has higher requirements on equipment, and has the defects of high reaction temperature, long time and high energy consumption. Although the methods have great progress in expanding the types of substrates, optimizing catalysts and reaction conditions, improving the yield of the benzopyrazine and the derivatives thereof, simplifying reaction steps, reducing environmental pollution and the like, the problems of expensive raw materials, low product yield and the like still exist, and meanwhile, most methods adopt complex homogeneous catalysts and are not beneficial to industrial production; the use of heterogeneous catalysts in small portions also uses large amounts of environmentally unfriendly organic solvents. Therefore, until now, in industry, benzopyrazines or substituted benzopyrazines are prepared by condensation using expensive 1, 2-dicarbonyl compounds and aromatic 1, 2-diamines as raw materials, which not only requires many reaction steps, but also requires troublesome separation of most of the products.
Therefore, it is necessary to find an efficient and environment-friendly method for synthesizing benzopyrazine and derivatives thereof by using an o-nitroaniline compound and aliphatic diol as raw materials under the action of a solid catalyst.
Disclosure of the invention
The first technical problem to be solved by the invention is to provide Cu-Pd-CeO 2 /γ-Al 2 O 3 @ NP catalysisThe preparation method of the agent.
The second technical problem to be solved by the invention is to provide a method for preparing the compound by using an o-nitroaniline compound and a fatty diol compound as raw materials in Cu-Pd-CeO 2 /γ-Al 2 O 3 Under the combined action of a @ NP catalyst and alkali, the method for efficiently synthesizing the benzopyrazine and the derivatives thereof by a one-pot method.
In order to solve the technical problems, the invention adopts the following technical scheme:
in a first aspect, the invention provides Cu-Pd-CeO 2 /γ-Al 2 O 3 Preparation method of @ NP catalyst and Cu-Pd-CeO 2 /γ-Al 2 O 3 In the @ NP catalyst, the total load of N and P is 1.2-4.8%; the loading amount of Cu is 0.5-5 wt%; the load capacity of Pd is 0.5-5 wt%; the loading amount of Ce is 5-15 wt%; the preparation method comprises the following steps:
(1) Taking a certain amount of gamma-Al 2 O 3 Adding deionized water and stirring to obtain slurry, heating to 70-90 ℃, adding cerium-containing compound solution with corresponding mass, stirring and dipping at the constant temperature of 70-90 ℃ for 2-6 h, dropwise adding ammonia water solution to adjust the pH value to 9-10, continuously stirring at the constant temperature for 2-6 h, cooling to room temperature and filtering, washing a filter cake to be neutral by using deionized water, drying at the temperature of 80-120 ℃ for 5-9 h under the air atmosphere, and roasting at the temperature of 600-800 ℃ for 2-4 h under the air atmosphere to obtain CeO 2 /γ-Al 2 O 3 A carrier;
(2) Taking a certain amount of CeO 2 /γ-Al 2 O 3 Adding the carrier into ammonium phosphate aqueous solution, stirring and dipping for 1-3 h at 30-50 ℃, drying for 5-9 h at 80-120 ℃ under air atmosphere, and roasting for 1-3 h at 400-600 ℃ under air atmosphere to obtain CeO 2 /γ-Al 2 O 3 The @ NP vector;
(3) Taking a certain amount of CeO 2 /γ-Al 2 O 3 Adding the @ NP carrier into deionized water, stirring to obtain slurry, heating to 60-100 ℃, adding palladium-containing compound solution and copper-containing compound solution with corresponding mass, stirring and soaking at constant temperature for 3-7 h; cooling to room temperature, adding alkaline solution dropwise to adjust pH to 8 toStirring for 0.5-1.5 h at constant temperature between 10 ℃, filtering, and washing a filter cake to be neutral by using deionized water; drying for 5-9 h at 80-120 ℃ under air atmosphere; then roasting for 2-6 h at 200-300 ℃ under air atmosphere, finally reducing for 1-3 h with hydrogen at 200-300 ℃ to obtain Cu-Pd-CeO 2 /γ-Al 2 O 3 @ NP catalyst.
The Cu-Pd-CeO of the invention 2 /γ-Al 2 O 3 The content of each element in the @ NP catalyst is calculated by taking the utilization rate of each element in the preparation process as 100 percent, and the load is the content of the element relative to gamma-Al 2 O 3 Is measured by mass percentage. Preferably, the Cu-Pd-CeO 2 /γ-Al 2 O 3 In the @ NP catalyst, the supported amount of Pd is 1 to 5wt%, more preferably 5wt%; the Cu loading is 1 to 5wt%, more preferably 3.5%; the amount of Ce supported is 5 to 15wt%, more preferably 10%.
Preferably, the palladium-containing compound is H 2 PdCl 4 、Pd(CH 3 COO) 2 Or Pd (NO) 3 ) 2 (ii) a The copper-containing compound is Cu (NO) 3 ) 2 Or CuCl 2 (ii) a The cerium-containing compound is CeCl 3 Or Ce (OH) 3 。
Preferably, in step (1), the γ -Al is 2 O 3 The feeding ratio of the deionized water to the deionized water is 5g:35-45mL.
Preferably, in the step (1), the concentration of the cerium-containing compound solution is 0.04-0.06g/mL in terms of Ce concentration.
Preferably, in step (2), the concentration of the aqueous solution of ammonium phosphate is from 0.002 to 0.0025g/mL. The dosage of the aqueous solution can be determined according to the required load of P + N.
Preferably, in step (3), ceO 2 /γ-Al 2 O 3 The dosage ratio of the @ NP carrier and the deionized water is determined by the dosage ratio of gamma-Al in the carrier 2 O 3 And the charge ratio of the deionized water is 5g:35-45mL.
Preferably, in the step (3), the concentration of the palladium-containing compound solution is 0.04 to 0.05g/mL in terms of the concentration of Pd, and the concentration of the copper-containing compound solution is 0.04 to 0.05g/mL in terms of the concentration of Cu.
Preferably, in the step (3), the alkaline solution is 0.05-0.15 g/ml NaOH aqueous solution and 0.05-0.15 g/ml NaHCO aqueous solution 3 Aqueous solution or 0.05-0.15 g/ml Na 2 CO 3 An aqueous solution.
In a second aspect, the invention provides a method for synthesizing benzopyrazines shown in formula (III) and derivatives thereof by a one-pot method, wherein an o-nitroaniline compound shown in formula (I) and a fatty diol compound shown in formula (II) are used as raw materials, and the raw materials are subjected to solvent-free conditions in the presence of Cu-Pd-CeO 2 /γ-Al 2 O 3 Synthesizing a benzopyrazine compound shown in a formula (III) by a one-pot method under the combined action of a @ NP catalyst and alkali;
wherein, X 1 、X 2 、X 3 、X 4 Each independently is hydrogen, methyl, ethyl or methoxy; r 1 、R 2 Each independently hydrogen, methyl or ethyl.
In the synthesis of the benzopyrazine compound, the Cu-Pd-CeO 2 /γ-Al 2 O 3 The mass ratio of the @ NP catalyst to the o-nitroaniline compound is 1:5 to 20, preferably 1:10.
in the synthesis of the benzopyrazine compound, the o-nitroaniline compound: fatty diol: the molar ratio of the alkali is 1:5 to 15:0.5 to 2, preferably 1:10:1.
in the synthesis of the benzopyrazines compound, the reaction temperature is 70-90 ℃, and the reaction time is 6-12 hours. Further, the reaction temperature is preferably 75 to 85 ℃.
In the synthesis of the benzopyrazine compound, the reaction is carried out in the air.
Specifically, the one-pot synthesis method of the benzopyrazine compounds is carried out as follows, firstly, cu-Pd-CeO 2 /γ-Al 2 O 3 The method comprises the following steps of putting @ NP, an o-nitroaniline compound (I), aliphatic diol (II) and alkali into a three-necked flask reactor, controlling the temperature in the reactor to be 75-85 ℃ for reaction, finishing the reaction after 6-12 hours, filtering and separating reaction materials to obtain a supported metal solid catalyst and filtrate, wherein the supported metal solid catalyst can be continuously reused, and extracting, distilling or rectifying the filtrate to obtain the benzopyrazine compound.
By adopting the synthesis method, the highest conversion rate of the o-nitroaniline compound serving as the raw material can reach 100 percent, and the highest yield of the target product benzopyrazines compound can reach 98 percent.
The beneficial effects of the invention are:
(1) The Cu-Pd-CeO of the invention 2 /γ-Al 2 O 3 The @ NP catalyst is prepared by doping N and P to increase the number of basic sites and load CeO 2 The catalyst helps to extract protons, thereby improving catalytic dehydrogenation activity and constructing a supported metal solid catalyst with high activity, good stability and easy separation.
(2) Compared with the traditional industrial production, the method for synthesizing the benzopyrazine and the derivatives thereof simplifies the production process, combines a plurality of steps of industrial production into a one-pot reaction, and simultaneously uses low-cost raw materials to reduce the production cost.
(2) Compared with the existing synthesis route, the method for synthesizing the benzopyrazine and the derivatives thereof has the advantages of high product yield, no use of environment-unfriendly organic solvent and no need of use of expensive alkali.
(3) The method for synthesizing the benzopyrazine and the derivatives thereof adopts Cu-Pd-CeO 2 /γ-Al 2 O 3 The catalyst of @ NP shortens the reaction time, reduces the reaction temperature, reduces the reaction energy consumption, obviously improves the product selectivity, does not consume transition metal and noble metal in the reaction process, is convenient to reuse, and is beneficial to industrial production.
(IV) detailed description of the preferred embodiments
The following specific examples illustrate the technical solutions of the present invention, but the scope of the present invention is not limited thereto;
examples one to three are examples of the preparation of supported metal solid catalysts:
example 1
5g of gamma-Al is taken 2 O 3 (aladdin # A102091) 35mL deionized water was added and stirred to a slurry, heated in a water bath to 70 deg.C, and 6.25mL Ce (OH) was added dropwise 3 Stirring and dipping the solution (0.04 g Ce/ml) at the constant temperature of 70 ℃ for 2h, dropwise adding an ammonia solution (25-28%) to adjust the pH value to 9-10, keeping the temperature of the solution and stirring for 2h; then cooling to room temperature, filtering, washing the filter cake to be neutral by deionized water; and drying at 80 ℃ for 5h in an air atmosphere; then roasting for 2 hours in the air atmosphere at the temperature of 600 ℃ to obtain CeO 2 5wt％ /γ-Al 2 O 3 Taking CeO 2 5wt％/γ-Al 2 O 3 Adding into 40ml 0.002g/ml ammonium phosphate aqueous solution, stirring and soaking at 30 deg.C for 1 hr, drying at 80 deg.C for 5 hr, and calcining at 400 deg.C for 1 hr to obtain CeO 2 5wt％/γ-Al 2 O 3 @ NP carrier, taking CeO 2 5wt％ /γ-Al 2 O 3 @ NP was stirred with 35mL of deionized water until a slurry was obtained, heated to 60 ℃ in a water bath, and 4.375mL of Pd (C2H 3O 2) 2 solution (0.04 g Pd/mL) and 1.875mL of CuCl were added dropwise 2 Soaking the solution (0.04 g Cu/ml) at 60 deg.C for 3 hr under stirring, cooling to 25 deg.C, and adding 0.1g/ml NaHCO dropwise 3 Adjusting the pH value of the aqueous solution to be between 8 and 10, and stirring for 0.5 hour; filtering, washing a filter cake to be neutral by using deionized water; and drying at 80 ℃ for 5h in an air atmosphere; then roasting for 2h in an air atmosphere at 200 ℃, and finally reducing for 1h in a hydrogen atmosphere at 200 ℃ to obtain the Cu1.5wt% -Pd3.5wt% -CeO 2 5wt％/γ-Al 2 O 3 @ NP catalyst.
Example 2
5g of gamma-Al is taken 2 O 3 (aladdin # A102091) 40mL deionized water is added and stirred to slurry, heated to 80 ℃ in a water bath, and 10mL CeCl is added dropwise 3 Stirring and dipping the solution (0.05 g Ce/ml) at the constant temperature of 80 ℃ for 4 hours, dropwise adding an ammonia solution (25-28%) to adjust the pH value to be between 9 and 10, and stirring the solution for 4 hours again while keeping the temperature of the solution; then cooling to room temperature, filtering, washing the filter cake to be neutral by deionized water; and is arranged atDrying for 7h at 100 ℃ in an air atmosphere; then roasting for 3 hours at 700 ℃ in air atmosphere to obtain CeO 2 10wt％ /γ-Al 2 O 3 (ii) a Taking CeO 2 10wt％/γ-Al 2 O 3 Adding into 32ml 0.0025g/ml ammonium phosphate water solution, stirring and soaking at 40 deg.C for 2 hr, drying at 100 deg.C for 7 hr, and calcining at 500 deg.C for 2 hr to obtain CeO 2 10wt％/γ-Al 2 O 3 @ NP carrier, taking CeO 2 10wt％ /γ-Al 2 O 3 @ NP added with 40mL deionized water and stirred to be serous fluid, heated to 80 ℃ in water bath, and respectively added with 5mL of H dropwise 2 PdCl 4 Solution (0.05 g Pd/ml), 3.5ml Cu (NO) 3 ) 2 Soaking the solution (0.05 g Cu/ml) at 80 deg.C under stirring for 5 hr, cooling to 25 deg.C, and adding 0.1g/ml Na dropwise 2 CO 3 Adjusting the pH value of the aqueous solution to 8-10, and stirring for 1h; then cooling to room temperature, filtering, washing the filter cake to be neutral by deionized water; and drying at 100 ℃ for 7h in an air atmosphere; then roasting for 4 hours in the air atmosphere at the temperature of 250 ℃, and finally reducing for 2 hours in the hydrogen atmosphere at the temperature of 250 ℃ to obtain the Cu3.5wt% -Pd5wt% -CeO 2 10wt％ /γ-Al 2 O 3 @ NP catalyst.
Example 3
5g of gamma-Al is taken 2 O 3 (aladdin # A102091) adding 45mL of deionized water, stirring to slurry, heating to 90 ℃ in a water bath, and adding 12.5mL of CeCl dropwise 3 Stirring and dipping the solution (0.06 g Ce/ml) at the constant temperature of 90 ℃ for 6h, dropwise adding an ammonia solution (25-28%) to adjust the pH value to be between 9 and 10, and stirring the solution for 6h again while keeping the temperature of the solution; then cooling to room temperature, filtering, washing the filter cake to be neutral by deionized water; and drying at 120 deg.C for 9h in air atmosphere; then roasting for 4 hours at 800 ℃ in the air atmosphere to obtain CeO 2 15wt％ /γ-Al 2 O 3 (ii) a Taking CeO 2 15wt％/γ-Al 2 O 3 Adding into 32ml 0.0025g/ml ammonium phosphate water solution, stirring and soaking at 50 deg.C for 3 hr, drying at 120 deg.C for 9 hr, and calcining at 600 deg.C for 3 hr to obtain CeO 2 15wt％/γ-Al 2 O 3 @ NP carrier, taking CeO 2 15wt％ /γ-Al 2 O 3 @ NP was stirred with 45mL of deionized water and heated to 100 ℃ in a water bath, and 5mL of Pd (NO) was added dropwise 3 ) 2 Solution (0.05 g Pd/ml), 5ml Cu (NO) 3 ) 2 Stirring and dipping the solution (0.05 g Cu/ml) at the constant temperature of 100 ℃ for 7 hours, cooling to 25 ℃, then dropwise adding 0.1g/ml NaOH aqueous solution to adjust the pH value to be between 8 and 10, stirring for 1.5 hours, filtering, and washing a filter cake to be neutral by deionized water; and drying at 120 deg.C for 9h in air atmosphere; then roasting for 6h in 300 ℃ air atmosphere, and finally reducing for 3h in 300 ℃ hydrogen atmosphere to obtain the Cu5wt% -Pd5wt% -CeO 2 15wt％/γ-Al 2 O 3 @ NP catalyst.
Examples 4 to 14 Cu-Pd-CeO prepared by the above-described methods 2 /γ-Al 2 O 3 @ NP, an example for the synthesis of benzopyrazines:
examples 4 to 6
Examples 4-6 examine the reaction results of one-pot synthesis of benzopyrazine compounds with various aliphatic diols using o-nitroaniline.
0.2g of the catalyst prepared in example 2 (Cu3.5wt% -Pd5wt% -CeO) 2 10wt％/γ-Al 2 O 3 @ NP), 2g of o-nitroaniline, 8ml of aliphatic diol, and 0.8g of potassium hydroxide were placed in a three-necked flask reactor. Heating to 80 ℃ and starting stirring (1000 r/min), stirring at constant temperature for reaction for 6 hours, stopping reaction, cooling to room temperature, filtering reaction liquid to separate the catalyst, extracting the filtrate, and analyzing by gas chromatography, wherein the experimental results are shown in table 1.
TABLE 1 one-pot reaction of o-nitroaniline with different aliphatic diols Experimental results
| Examples | Aliphatic diols | Conversion (%) | Product of | Selectivity (%) |
| 4 | Ethylene glycol | 100 | Benzopyrazines | 98.3 |
| 5 | 1, 2-propanediol | 100 | 2-methylbenzopyrazines | 94.7 |
| 6 | 2, 3-butanediol | 100 | 2, 3-dimethyl-benzopyrazines | 93.1 |
Example 7
Example 7 investigates the effect influence of increasing the catalyst amount and improving the yield of the benzopyrazines compound.
0.4g of the catalyst prepared in example 2 (Cu3.5wt% -Pd5wt% -CeO) 2 10wt％/γ-Al 2 O 3 @ NP), 2g of o-nitroaniline, 8ml of ethylene glycol, and 0.8g of potassium hydroxide were placed in a three-necked flask reactor. Heating to 80 ℃, starting stirring (1000 r/min), stirring at constant temperature for reaction for 6 hours, stopping the reaction, cooling to room temperature, filtering the reaction liquid to separate the catalyst, extracting the filtrate, and analyzing by gas chromatography, wherein the conversion rate of the o-nitroaniline is 100%, and the selectivity of the target product benzopyrazine is 97.5%.
Examples 8 to 10
Examples 8-10 examine the reaction results of synthesizing benzopyrazines by one-pot method of ethylene glycol and different o-nitroaniline compounds.
0.2g of the catalyst prepared in example 2 (Cu3.5wt% -Pd5wt% -CeO) 2 10wt％/γ-Al 2 O 3 @ NP), 2g of an o-nitroaniline compound, 8ml of ethylene glycol and 0.8g of an alkali were placed in a three-necked flask reactor. Heating to 80 ℃ and stirring (1000 r/min), stirring at constant temperature for 6h, stopping reaction, cooling to room temperature, filtering reaction liquid to separate the catalyst, extracting the filtrate, and analyzing by gas chromatography, wherein the experimental results are shown in Table 2.
TABLE 2 one-pot reaction of ethylene glycol with different o-nitroanilides
| Examples | O-nitroanilides | Conversion (%) | Product of | Selectivity (%) |
| 8 | 4-methyl-2-nitroaniline | 100 | 6-methylquinoxaline | 90.9 |
| 9 | 4-Ethyl-2-nitroaniline | 100 | 6-ethylquinoxaline | 89.6 |
| 10 | 3-methyl-2-nitroaniline | 100 | 5-methylquinoxaline | 86.2 |
Examples 11 to 14
Examples 11-14 examine the reaction results of one-pot synthesis of benzopyrazines from ethylene glycol and o-nitroaniline in the presence of different catalysts.
2g of o-nitroaniline, 8ml of ethylene glycol and 0.8g of potassium hydroxide were placed in a three-necked flask reactor, and the catalysts were the catalysts prepared in examples 1,2 and 3 and the catalyst recovered after the reaction in example 4, and the amount of the catalyst used was 0.2g. Heating to 80 ℃, starting stirring (1000 r/min), stirring at constant temperature for reaction for 6 hours, stopping the reaction, cooling to room temperature, filtering the reaction liquid to separate the catalyst, extracting the filtrate, and analyzing by gas chromatography, wherein the experimental result is shown in table 3, and the target product is the benzopyrazine.
TABLE 3 Experimental results of one-pot reaction of ethylene glycol and o-nitroaniline under different catalysts
| Examples | Catalyst and process for preparing same | Conversion (%) | Selectivity (%) |
| 11 | Example 1 | 100 | 94.5 |
| 12 | Example 2 | 100 | 98.3 |
| 13 | Example 3 | 100 | 96.1 |
| 14 | Example 4 recovered catalyst | 100 | 97.2 |
Comparative example 1
5g of gamma-Al is taken 2 O 3 (aladdin # A102091) 40ml deionized water is added and stirred to slurry, heated to 80 ℃ in water bath, and 5ml Pd (C) is respectively added dropwise 2 H 3 O 2 ) 2 Solution (0.05 g Pd/ml), 3.5ml CuCl 2 Soaking the solution (0.05 g Cu/ml) at 80 deg.C under stirring for 5 hr, cooling, and adding 0.1g/ml Na dropwise 2 CO 3 Adjusting the pH value of the aqueous solution to 8-10, and stirring for 1h; filtering, washing a filter cake to be neutral by using deionized water; and drying at 100 ℃ for 7h in an air atmosphere; then roasting for 4 hours in the air atmosphere at 250 ℃, and finally reducing for 2 hours in the hydrogen atmosphere at 250 ℃ to obtain the Cu3.5wt% -Pd5 wt%/gamma-Al 2 O 3 A catalyst.
Comparative example 2
5g of gamma-Al is taken 2 O 3 (aladdin # A102091) 40ml deionized water was added and stirred to a slurry, heated in a water bath to 80 ℃ and 10ml CeCl was added dropwise 3 Stirring and dipping the solution (0.05 g Ce/ml) at the constant temperature of 80 ℃ for 4 hours, dropwise adding an ammonia solution (25-28%) to adjust the pH value to 9-10, keeping the temperature of the solution and stirring for 4 hours; then cooling to room temperature, filtering, washing the filter cake to be neutral by deionized water; and drying at 100 ℃ for 7h in an air atmosphere; then roasting for 3 hours at 700 ℃ in air atmosphere to obtain CeO 2 10wt％ /γ-Al 2 O 3 (ii) a Taking CeO 2 10wt％/γ-Al 2 O 3 Adding 40ml deionized water, stirring to obtain slurry, heating in water bath to 80 deg.C, and respectively dropwise adding 5ml H 2 PdCl 4 Solution (0.05 g Pd/ml), 3.5ml Cu (NO) 3 ) 2 Soaking the solution (0.05 g Cu/ml) at 80 deg.C under stirring for 5 hr, cooling, and adding 0.1g/ml Na dropwise 2 CO 3 Adjusting the pH value of the aqueous solution to 8-10, and stirring for 1h; then cooling to room temperature, filtering, washing the filter cake to be neutral by deionized water; and drying at 100 ℃ for 7h in an air atmosphere; then roasting for 4 hours in the air atmosphere at 250 ℃, and finally reducing for 2 hours in the hydrogen atmosphere at 250 ℃ to obtain the Cu3.5wt% -Pd5wt% -CeO 2 10wt％ /γ-Al 2 O 3 A catalyst.
Comparative example 3
5g of gamma-Al is taken 2 O 3 (aladdin # A102091) is added into 32ml 0.0025g/ml ammonium phosphate water solution, stirred and dipped for 2h at 40 ℃, dried for 7h at 100 ℃, and roasted for 2h at 500 ℃ to obtain gamma-Al 2 O 3 The @ NP carrier being gamma-Al 2 O 3 @ NP was added 40ml of deionized water and stirred to a slurry, heated to 80 ℃ in a water bath, and 5ml of H was added dropwise 2 PdCl 4 Solution (0.05 g Pd/ml), 3.5ml Cu (NO) 3 ) 2 Soaking the solution (0.05 g Cu/ml) at 80 deg.C under stirring for 5 hr, cooling, and adding 0.1g/ml Na dropwise 2 CO 3 Adjusting the pH value of the aqueous solution to 8-10, and stirring for 1h; then cooling to room temperature, filtering, washing the filter cake to be neutral by deionized water; and drying at 100 ℃ for 7h in an air atmosphere; then roasting for 4 hours in an air atmosphere at 250 ℃, and finally reducing for 2 hours in a hydrogen atmosphere at 250 ℃ to obtain the Cu3.5wt% -Pd5 wt%/gamma-Al 2 O 3 @ NP catalyst.
Comparative example 4
5g of gamma-Al is taken 2 O 3 (aladdin # A102091) 40mL deionized water is added and stirred to slurry, heated to 80 ℃ in a water bath, and 10mL CeCl is added dropwise 3 Stirring and dipping the solution (0.05 g Ce/ml) at the constant temperature of 80 ℃ for 4 hours, dropwise adding an ammonia solution (25-28%) to adjust the pH value to be between 9 and 10, and stirring the solution for 4 hours again while keeping the temperature of the solution; then cooling to room temperature, filtering, washing the filter cake to be neutral by deionized water; and drying at 100 ℃ for 7h in an air atmosphere; then roasting for 3 hours in the air atmosphere at 700 ℃ to obtain CeO 2 10wt％ /γ-Al 2 O 3 (ii) a Taking CeO 2 10wt％/γ-Al 2 O 3 Adding into 32ml 0.0025g/ml ammonium phosphate water solution, stirring and soaking at 40 deg.C for 2 hr, drying at 100 deg.C for 7 hr, and calcining at 500 deg.C for 2 hr to obtain CeO 2 10wt％/γ-Al 2 O 3 @ NP carrier, taking CeO 2 10wt％ /γ-Al 2 O 3 @ NP added with 40mL deionized water and stirred to slurry, heated to 80 ℃ in water bath, and 5mL H is added dropwise 2 PdCl 4 Soaking the solution (0.05 g Pd/ml) at 80 deg.C under stirring for 5 hr, cooling, and adding 0.1g/ml Na dropwise 2 CO 3 Adjusting the pH value of the aqueous solution to 8-10, and stirring for 1h; then cooling to room temperature, filtering, washing the filter cake to be neutral by deionized water; and drying at 100 ℃ for 7h in an air atmosphere; then roasting for 4 hours in air atmosphere at 250 ℃, and finally reducing for 2 hours in hydrogen atmosphere at 250 ℃ to obtain Pd5wt% -CeO 2 10wt％/γ-Al 2 O 3 @ NP catalyst.
Comparative example 5
5g of gamma-Al is taken 2 O 3 (aladdin # A102091) 40mL deionized water is added and stirred to slurry, heated to 80 ℃ in a water bath, and 10mL CeCl is added dropwise 3 Stirring and dipping the solution (0.05 g Ce/ml) at the constant temperature of 80 ℃ for 4 hours, dropwise adding an ammonia solution (25-28%) to adjust the pH value to be between 9 and 10, and stirring the solution for 4 hours again while keeping the temperature of the solution; then cooling to room temperature, filtering, washing the filter cake to be neutral by deionized water; and drying at 100 ℃ for 7h in an air atmosphere; then roasting for 3 hours in the air atmosphere at 700 ℃ to obtain CeO 2 10wt％ /γ-Al 2 O 3 (ii) a Taking CeO 2 10wt％/γ-Al 2 O 3 Adding into 32ml 0.0025g/ml ammonium phosphate water solution, stirring and soaking at 40 deg.C for 2 hr, drying at 100 deg.C for 7 hr, and calcining at 500 deg.C for 2 hr to obtain CeO 2 10wt％/γ-Al 2 O 3 @ NP carrier, taking CeO 2 10wt％ /γ-Al 2 O 3 @ NP was stirred with 40mL of deionized water, heated to 80 ℃ in a water bath, and 3.5mL of Cu (NO) was added dropwise 3 ) 2 Soaking the solution (0.05 g Cu/ml) at 80 deg.C under stirring for 5 hr, cooling, and adding 0.1g/ml Na dropwise 2 CO 3 Adjusting the pH value of the aqueous solution to 8-10, and stirring for 1h; then cooling to room temperature, filtering, washing the filter cake to be neutral by deionized water; and drying at 100 ℃ for 7h in an air atmosphere; then roasting for 4 hours in the air atmosphere at the temperature of 250 ℃, and finally reducing for 2 hours in the hydrogen atmosphere at the temperature of 250 ℃ to obtain Cu3.5wt% -CeO 2 10wt％/γ-Al 2 O 3 @ NP catalyst.
The catalysts prepared in comparative examples 1 to 5 above were used for the following reactions, respectively:
2g of o-nitroaniline, 8ml of ethylene glycol, 0.8g of potassium hydroxide and a catalyst are put into a three-neck flask reactor. Heating to 80 ℃, starting stirring (1000 r/min), stirring at constant temperature for reaction for 6 hours, stopping the reaction, cooling to room temperature, filtering the reaction liquid to separate the catalyst, extracting the filtrate, and analyzing by gas chromatography, wherein the experimental result is shown in table 4, and the target product is the benzopyrazine.
TABLE 4 Experimental results of one-pot reaction of ethylene glycol with o-nitroaniline over different catalysts
Claims (13)
1. Cu-Pd-CeO 2 /γ-Al 2 O 3 Preparation method of @ NP catalyst and Cu-Pd-CeO 2 /γ-Al 2 O 3 In the @ NP catalyst, the total load of N and P is 1.2-4.8%; the loading amount of Cu is 0.5-5 wt%; the load capacity of Pd is 0.5-5 wt%; the loading amount of Ce is 5-15 wt%; the preparation method comprises the following steps:
(1) Taking a certain amount of gamma-Al 2 O 3 Adding deionized water and stirring to obtain slurry, heating to 70-90 ℃, adding cerium-containing compound solution with corresponding mass, stirring and dipping at the constant temperature of 70-90 ℃ for 2-6 h, dropwise adding ammonia water solution to adjust the pH value to 9-10, continuously stirring at the constant temperature for 2-6 h, cooling to room temperature and filtering, washing a filter cake to be neutral by using deionized water, drying at the temperature of 80-120 ℃ for 5-9 h under the air atmosphere, and roasting at the temperature of 600-800 ℃ for 2-4 h under the air atmosphere to obtain CeO 2 /γ-Al 2 O 3 A carrier;
(2) Taking a certain amount of CeO 2 /γ-Al 2 O 3 Adding the carrier into ammonium phosphate aqueous solution, stirring and dipping for 1-3 h at 30-50 ℃, drying for 5-9 h at 80-120 ℃ under air atmosphere, and roasting for 1-3 h at 400-600 ℃ under air atmosphere to obtain CeO 2 /γ-Al 2 O 3 The @ NP vector;
(3) Taking a certain amount of CeO 2 /γ-Al 2 O 3 Adding the @ NP carrier into deionized water, stirring to obtain slurry, heating to 60-100 ℃, adding palladium-containing compound solution and copper-containing compound solution with corresponding mass, stirring and soaking at constant temperature for 3-7 h; cooling to room temperature, then dropwise adding an alkaline solution to adjust the pH value to be between 8 and 10, stirring at constant temperature for 0.5 to 1.5 hours, filtering, and washing a filter cake to be neutral by using deionized water; drying for 5-9 h at 80-120 ℃ under air atmosphere; then roasting for 2-6 h at 200-300 ℃ under air atmosphere, finally reducing for 1-3 h with hydrogen at 200-300 ℃ to obtain Cu-Pd-CeO 2 /γ-Al 2 O 3 @ NP catalyst.
2. The method of claim 1, wherein: the Cu-Pd-CeO 2 /γ-Al 2 O 3 In the @ NP catalyst, the loading amount of Pd is 1-5 wt%, the loading amount of Cu is 1-5 wt%, and the loading amount of Ce is 10%.
3. The method of claim 2, wherein: the Cu-Pd-CeO 2 /γ-Al 2 O 3 In the @ NP catalyst, the Pd loading was 5wt%.
4. The method of claim 2, wherein: the Cu-Pd-CeO 2 /γ-Al 2 O 3 In the @ NP catalyst, the Cu supporting amount was 3.5%.
5. The method of claim 1, wherein: the palladium-containing compound is H 2 PdCl 4 、Pd(CH 3 COO) 2 Or Pd (NO) 3 ) 2 (ii) a The copper-containing compound is Cu (NO) 3 ) 2 Or CuCl 2 (ii) a The cerium-containing compound is CeCl 3 Or Ce (OH) 3 。
6. The method of claim 1, wherein: in the step (1), the gamma-Al 2 O 3 The feeding ratio of the deionized water to the deionized water is 5g:35-45mL, and the concentration of the cerium-containing compound solution is 0.04-0.06g/mL calculated by the concentration of Ce.
7. The method of claim 1, wherein: in the step (2), the concentration of the ammonium phosphate aqueous solution is 0.002-0.0025g/mL.
8. The method of claim 1, wherein: in step (3), ceO 2 /γ-Al 2 O 3 The ratio of the dosage of the @ NP carrier and the deionized water is that gamma-Al is added 2 O 3 And the charge ratio of the deionized water is 5g:35-45mL, the concentration of the palladium-containing compound solution is 0.04-0.05g/mL calculated by the concentration of Pd, and the concentration of the copper-containing compound solution is 0.04-0.05g/mL calculated by the concentration of Cu.
9. The method of claim 1, wherein: in the step (3), the alkaline solution is 0.05 to 0.15gml NaOH aqueous solution, 0.05-0.15 g/ml NaHCO 3 Aqueous solution or 0.05-0.15 g/ml Na 2 CO 3 An aqueous solution.
10. A method for synthesizing benzopyrazine shown as a formula (III) and derivatives thereof by a one-pot method, wherein an o-nitroaniline compound shown as a formula (I) and an aliphatic diol compound shown as a formula (II) are used as raw materials, and the Cu-Pd-CeO is prepared by the method according to claim 1 under the solvent-free condition 2 /γ-Al 2 O 3 Synthesizing a benzopyrazine compound shown in a formula (III) by a one-pot method under the combined action of a @ NP catalyst and alkali;
wherein, X 1 、X 2 、X 3 、X 4 Each independently is hydrogen, methyl, ethyl or methoxy; r is 1 、R 2 Each independently hydrogen, methyl or ethyl.
11. The method of claim 10, wherein: the Cu-Pd-CeO 2 /γ-Al 2 O 3 The mass ratio of the @ NP catalyst to the o-nitroaniline compound is 1:5 to 20; the o-nitroaniline compound: fatty diol: the molar ratio of the alkali is 1:5 to 15:0.5 to 2.
12. The method of claim 10, wherein: the reaction temperature is 70-90 ℃; the reaction time is 6 to 12 hours.
13. The method of claim 12, wherein: the reaction temperature is 75-85 ℃.
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